Since colossal ionic conductivity was detected in the planar heterostructures consisting of fluorite and perovskite, heterostructures have drawn great research interest as potential electrolytes for solid oxide fuel cells (SOFCs). However, so far, the practical uses of such promising material have failed to materialize in SOFCs due to the short circuit risk caused by SrTiO₃. In this study, a series of fluorite/perovskite heterostructures made of Sm-doped CeO₂ and SrTiO₃ (SDC–STO) are developed in a new bulk-heterostructure form and evaluated as electrolytes. The prepared cells exhibit a peak power density of 892 mW cm⁻² along with open circuit voltage of 1.1 V at 550 °C for the optimal composition of 4SDC–6STO. Further electrical studies reveal a high ionic conductivity of 0.05–0.14 S cm⁻¹ at 450–550 °C, which shows remarkable enhancement compared to that of simplex SDC. Via AC impedance analysis, it has been shown that the small grain-boundary and electrode polarization resistances play the major roles in resulting in the superior performance. Furthermore, a Schottky junction effect is proposed by considering the work functions and electronic affinities to interpret the avoidance of short circuit in the SDC–STO cell. Our findings thus indicate a new insight to design electrolytes for low-temperature SOFCs.

Semiconducting-ionic conductors have been recently described as excellent electrolyte membranes for low-temperature operation solid oxide fuel cells (LT-SOFCs). In the present work, two new functional materials based on zinc oxide (ZnO)—a legacy material in semiconductors but exceptionally novel to solid state ionics—are developed as membranes in SOFCs for the first time. The proposed ZnO and ZnO-LCP (La/Pr doped CeO₂) electrolytes are respectively sandwiched between two Ni_0.8Co_0.15Al_0.05Li-oxide (NCAL) electrodes to construct fuel cell devices. The assembled ZnO fuel cell demonstrates encouraging power outputs of 158–482 mW cm⁻² and high open circuit voltages (OCVs) of 1–1.06 V at 450–550 °C, while the ZnO-LCP cell delivers significantly enhanced performance with maximum power density of 864 mW cm⁻² and OCV of 1.07 V at 550 °C. The conductive properties of the materials are investigated. As a consequence, the ZnO electrolyte and ZnO-LCP composite exhibit extraordinary ionic conductivities of 0.09 and 0.156 S cm⁻¹ at 550 °C, respectively, and the proton conductive behavior of ZnO is verified. Furthermore, performance enhancement of the ZnO-LCP cell is studied by electrochemical impedance spectroscopy (EIS), which is found to be as a result of the significantly reduced grain boundary and electrode polarization resistances. These findings indicate that ZnO is a highly promising alternative semiconducting-ionic membrane to replace the electrolyte materials for advanced LT-SOFCs, which in turn provides a new strategic pathway for the future development of electrolytes.